CN101148618B - Diesel fuel additives containing cerium or manganese and detergents - Google Patents

Diesel fuel additives containing cerium or manganese and detergents Download PDF

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Publication number
CN101148618B
CN101148618B CN2007101034768A CN200710103476A CN101148618B CN 101148618 B CN101148618 B CN 101148618B CN 2007101034768 A CN2007101034768 A CN 2007101034768A CN 200710103476 A CN200710103476 A CN 200710103476A CN 101148618 B CN101148618 B CN 101148618B
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fuel
diesel
manganese
cerium
additive
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CN101148618A (en
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J·W·罗斯
D·理查森
D·J·克莱顿
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Afton Chemical Corp
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Afton Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/106—Liquid carbonaceous fuels containing additives mixtures of inorganic compounds with organic macromolecular compounds
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    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/12—Inorganic compounds
    • C10L1/1233—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof
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    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
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    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/12—Use of additives to fuels or fires for particular purposes for improving the cetane number
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    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/18—Use of additives to fuels or fires for particular purposes use of detergents or dispersants for purposes not provided for in groups C10L10/02 - C10L10/16
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
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    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1981—Condensation polymers of aldehydes or ketones
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    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
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    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1988—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid epoxy resins and derivatives; natural resins, e.g. colophony
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    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/23—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites
    • C10L1/231—Organic compounds containing nitrogen containing at least one nitrogen-to-oxygen bond, e.g. nitro-compounds, nitrates, nitrites nitro compounds; nitrates; nitrites
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    • C10L1/22—Organic compounds containing nitrogen
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    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
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Abstract

Provided herein is a diesel fuel additive composition comprising cerium oxide nanoparticles, optionally a manganese compound, a detergent, and a demulsifier. In one embodiment, the demulsifier has relatively low phosphorus concentration to thereby improve the solubility of the components and the thermal stability and clarity of the resulting diesel fuel. Also provided are methods for improving fuel economy, reducing smoke production, inhibiting deposition of sludge, and improving storage stability.

Description

The diesel-fuel additive that contains cerium or manganese and washing composition
Technical field
This specification sheets relates to the diesel fuel additive of the fuel stability of giving burning that finished diesel fuel machine fuel improves and raising.
Background technology
In diesel-fuel, used cerium oxide nanoparticles as the convertor catalyzer of eliminating the poisonous fume discharge.Cerium oxide is also having application aspect the particle emission that reduces diesel motor.Envirox TMFuel Borne Catalyst is a kind of diesel-fuel ignition dope that reduces fuel consumption and reduce the harmful exhaust discharging.
Have been found that some organometallic compound is effective as the ignition dope of distillate fuel such as household fuel wet goods.For example, U.S. Pat 3,112,789 have described cyclopentadienyl tricarbonyl manganese have been used for this purpose, and methyl cyclopentadienyl tricarbonyl manganese (MMT) compound are sold as this type of ignition dope that distillates fuel with the form of the solution in hydrocarbon diluent.Two (cyclopentadienyl) iron is also as ignition dope propaganda and the sale used for this fuel.
U.S. Pat 3,883,320 and US3,891,401 have instructed the salt that adds transition metal such as manganese and alkaline-earth metal such as calcium in jet fuel to reduce settling and cigarette.Manganese/calcium the weight ratio of these patents needs about 5/1 and the metal group resultant of 200-600ppm are (in ' 401 patents, 200-500ppm).
Yet, in some additive combination preparation diesel-fuel, can encounter difficulties, thereby cause muddiness, precipitation, insoluble, inadequate fuel economy and inadequate cigarette to reduce.Appearance is to the demand of hydrocarbon matter fuel with the compositions of additives that dissolves in fuel, the dust that described composition produces in the time of not only can reducing fuel combustion, cigarette and/or carbonaceous product, and can improve the solvability in fuel and improve the fuel economy that fuel combustion produces.In this demand of realization, it also is important that a kind of like this additive is provided, this additive prevents from or suppresses residue at least to be deposited on the crucial engine or burner part or surface, and the fuel composition with gratifying physicals such as thermostability and stability in storage is provided.It also is extremely desirable that a kind of like this compositions of additives is provided, said composition can reduce or be suppressed at the toxic discharge (for example, carbon monoxide, unburned hydrocarbon, polyaromatic and/or particulate) that forms when using fuel in engine or burner or the similar combustion unit.It also is very desirable purpose that the compositions of additives that can reduce fuel consumption is provided.Therefore, there are the improved diesel-fuel additive of the fuel economy that reduces and improve for the organo-metallic fuel dope solvability of the burning that raising is provided, raising, the turbidity of reduction, improved cigarette and the needs of diesel-fuel additive combination.
Summary of the invention
An embodiment of Ti Chuing provides the diesel-fuel additive that contains cerium source such as cerium oxide particle or nano particle and diesel-fuel washing composition combination herein.
In one embodiment, diesel-fuel additive combination oxidation-containing cerium nano particle, cetane number improver, diesel-fuel washing composition and demulsifying compound.More particularly; another embodiment can oxidation-containing cerium particle or nano particle, contain diesel-fuel washing composition/dispersion agent, the demulsifying compound of alkylating (HR-PIB) succinimide polyamine and cetane number improver (for example nitric acid 2-ethylhexyl), can also the containing metal deactivator.
In one embodiment, can use the additive combination of oxidation-containing cerium particle or nano particle to handle diesel-fuel with the processing rate (treat rate) of the about 200ppm of about 1-in diesel-fuel.It is desirable that higher and cerium oxide lower aq is used for some.
Diesel-fuel additive combination of the present invention can also contain blended metal ignition dope such as cerium/manganese and cerium/manganese/iron cpd, alloy or mixture.The alloy that embodiment is herein used form of nanoparticles or contained two or more metals of nano particle improves solvability or the dispersiveness in fuel.
Another embodiment herein provides the diesel-fuel of oxidation-containing cerium nano particle, cetane number improver and washing composition and low-phosphorous demulsifying compound.
In another embodiment in this article, propose a kind of method that improves the efficient of diesel fuel for internal combustion engines machine fuel, in this fuel, add the diesel-fuel additive combination of oxidation-containing cerium nano particle, washing composition and demulsifying compound before this method is included in and is incorporated into fuel in the vehicles that comprise oil engine or other device.
Other embodiment herein comprises method, the method that improves diesel-fuel stability, the method that reduces cigarette in the diesel combustion that improve diesel-fuel efficient (fuel economy), improve the deliquescent method of organo-metallic fuel dope in diesel-fuel, reduce the turbidity of diesel-fuel with diesel-fuel additive method, reduce foamy method in the diesel-fuel and reduce the method for the filter stoppage of filter for diesel fuel.
Should be understood that: top general introduction and following detailed all are exemplary with illustrative, are the further explanations that is used to provide as the present invention for required protection.
Embodiment
In one embodiment, the invention provides a kind of solvable diesel-fuel additive combination that maybe can be scattered in cerium oxide particle in the diesel-fuel or nano particle that contains.More importantly, in one embodiment, the diesel-fuel additive combination contains the demulsifying compound compound to reduce or eliminate at pumping, distribution, filling jar and to use and add usually observed foam and/or emulsion problem in the thinner diesel-fuel.
In one embodiment, the demulsifying compound that uses in this diesel-fuel additive has the phosphorus content greater than 30 mg/kg demulsifying compounds.Yet, have been found that at present phosphorus content by reducing demulsifying compound in the diesel-fuel additive (no matter be have a mind to exist or exist with the form of pollutent) has improved fuel additive composition greatly and the stability of the fuel that obtains, and turbidity reduces obviously.Therefore, can in demulsifying compound, use the phosphorus content of about 30 mg/kg at most, or use the phosphorus content of about 24 mg/kg, in another embodiment, use the phosphorus of about 8 mg/kg, in another prescription, in the diesel-fuel demulsifying compound, use about 0.12 mg/kg phosphorus content.Along with phosphorus content descends, obtaining astonishing and unexpected improvement aspect turbidity reduction and the fuel stability.
Demulsifying compound herein (or cleaning agent) can be any one commercially available material, such as but not limited to oxyalkylated novolac polymer, as with commercially available those of the title of " NALCO " (trade mark) 7007 (not comprising Nalco) and " TOLAD " (trade mark) 2683 (not comprising Petrolite), alkylating phenol and by its deutero-resin, the alkyl phenol resin of-oxylization (oxylated) and yuban with 4-(1, the 1-dimethyl ethyl) phenol, propylene oxide (methyloxirane) and oxyethane, the EO/PO resin of ethoxylation, macrogol ester, ethylene oxide resin.
Therefore, this paper proposes a kind of diesel-fuel additive combination of oxidation-containing cerium nano particle, described cerium oxide nanoparticles has usually and is no more than 1 micron size, be no more than 300 nanometers in one embodiment, 1-300 nanometer for example, for example 1-150 nanometer, particularly 1-50 nanometer, especially 1-20 nanometer.This diesel-fuel additive combination can also contain at least a diesel-fuel washing composition/dispersion agent that is selected from succinimide, Mannich base, acid amides, amine and the polyetheramine.
In addition, this diesel-fuel additive combination can contain phosphorus content and reduce, for example the highest about 24 mg/kg, or about 8 mg/kg-Yue 24 mg/kg, or the demulsifying compound of about 0.1 mg/kg-Yue 8 mg/kg. obtained by this way to give the diesel-fuel additive combination that the outstanding turbidity decline of diesel-fuel, the raising of additive solvability, fuel stability raising, cigarette minimizing, combustion modifications and fuel economy improve.
Another benefit of the present invention is that demulsifying compound is with regard to its improved performance with regard to the performance of expecting in fuel dope and the finished product fuel.Therefore in having the fuel of washing composition/dispersion agent, be easy to form milk sap, need demulsifying compound. make the demulsifying compound passivation or all reduce the emulsion breaking effect, thereby cause more emulsification with any reaction of demulsifying compound reaction.Thereby provide a kind of method to improve the deemulsification of fuel dope by this way, this method comprises add cerium oxide nanoparticles, washing composition and demulsifying compound in fuel dope, wherein demulsifying compound has the phosphorus less than about 30 mg/kg. in another embodiment, this demulsifying compound has the phosphorus of the highest about 24 mg/kg, or the phosphorus that in an independent embodiment, has about 8 mg/kg-Yue 24 mg/kg, or In yet another embodiment, has the phosphorus of about 0.1 mg/kg-Yue 8 mg/kg.
The amount of cerium oxide nanoparticles, washing composition and the demulsifying compound that uses in present disclosed embodiment can change according to other required component in the character of required purposes, diesel-fuel and additive combination or the finished product fuel.
A kind of diesel fuel composition that contains the compositions of additives of a large amount of diesel-fuels and less improvement quantity combusted is provided in another embodiment, this compositions of additives comprises: a) one or more dissolve in the component of fuel, comprise in manganese and/or cerium compound, mixture or the alloy one or more; B) one or more dissolve in washing composition fuel, alkali metal containing or alkaline-earth metal, neutral or alkaline basic metal or the alkaline earth salts of one or more in for example at least a sulfonic acid and/or at least a carboxylic acid and/or at least a Whitfield's ointment and/or at least a alkylphenol and/or at least a sulfurized alkylphenol; And c) demulsifying compound that reduces as the phosphorus content that limits above, wherein component a) thinks that fuel provides the amount of 0.1-5ppm manganese, cerium or manganese and cerium to have components b) think that fuel composition provides the amount of 5-50ppm basic metal and/or alkaline-earth metal to exist.This embodiment can also contain one or more alkyl nitrate ester selected cetane number improvers.
The existence that has been found that washing composition/dispersion agent can make cerium oxide particle stable in fuel or fuel dope combination. and the special washing composition that can use in the present invention comprises the nitrogenous washing composition of alkalescence.Suitable ashless washing composition/dispersion agent comprises acid amides, amine, polyetheramine, Mannich base and preferred succinimide, although metallic in this article washing composition also is effective.
In many patent specifications, all described these dispersion agents, mainly be to use for lubricant compositions, but also described their uses in hydrocarbon fuel as additive.Ashless dispersion agent stays metallic resistates hardly or not when burning.They are only carbon containing, hydrogen, oxygen usually, and are in most of the cases also nitrogenous, but also contain other non-metallic element such as phosphorus, sulphur or boron sometimes.Useful especially in this article ashless dispersant/washing composition be by with the maleic anhydride of polyamine reaction on " hyperergy " polyisobutene (HR-PIB) of replacing and obtaining, thereby realize the dispersiveness of content to obtain to improve of about 5.4% nitrogen.This material is with HiTEC (R)4007 purchase the Corporation in Afton Chemical.In the fuel dope combination of this paper, can use washing composition/dispersion agent with the content of about 20% weight of about 5-.
In one embodiment, washing composition is the succinimide that each molecule on average has at least 3 nitrogen-atoms.Succinimide is preferably aliphatic, can be saturated or undersaturated, and especially olefinic is undersaturated, for example the alkyl or alkenyl succinimide.Washing composition generally is to be formed by the alkylene polyamine mixture that the alkyl or alkenyl amber acylation agent that has at least 35 carbon atoms in alkyl or alkenyl usually and each molecule on average have at least 3 nitrogen-atoms.In another embodiment, polyamine has 4-6 nitrogen-atoms at each molecule.Preferably; it can be by being 500-10 derived from number-average molecular weight, the polyisobutenyl amber acylation agent of 000 polyisobutene and can comprise ring-type and non-annularity part, ethylidene polyamines with the average composition from the Triethylenetetramine (TETA) to the penten form.Therefore, chain generally has 500-2500, and the molecular weight of 750-1500 especially, and the chain with molecular weight of about 900 and 1300 is useful especially is that the succinimide of about 2100 aliphatic chain also is useful although have molecular weight.At US-A-5, can find more details in 932,525 and 6048373 and EP-A-432,941,460309 and 1,237,373.
The example of useful in this article suitable containing metal washing composition includes but not limited to such as following material: phenol lithium, sodium phenylate, potassium phenylate, calcium phenylate, phenol magnesium, sulfurized phenol lithium, sulfurized sodium phenylate, sulfurized potassium phenylate, sulfurized calcium phenylate and sulfurized phenol magnesium, wherein each aryl has one or more fatty group, thereby gives the hydrocarbon solvability; Any subsalt (usually being called " high alkalinity " phenolate or " high alkalinity sulfuration phenolate ") in above-mentioned phenol or the sulfuration phenol; Sulfonic acid lithium, sodium sulfonate, potassium sulfonate, calcium sulphonate and sulfonic acid magnesium, wherein each sulfonic acid partly invests and contains usually on the substituent aromatic proton of one or more aliphatics, thereby gives the hydrocarbon solvability; Any subsalt in the above-mentioned sulfonate (usually being called " overbased sulfonate "); Lithium salicylate, sodium salicylate, potassium salicylate, calcium salicylate and magnesium salicylate, thus wherein the aromatics part is given the hydrocarbon solvability by one or more aliphatics substituting groups replacements usually; Any subsalt in the above-mentioned salicylate (usually being called " high alkaline salicylate "); Have 10-2000 carbon atom hydrolysis sulphur phosphatization (phosphosulphurised) alkene or have the hydrolysis phosphorus sulfurized alcohol of 10-2000 carbon atom and/or lithium, sodium, potassium, calcium and the magnesium salts of the phenolic compound that aliphatics replaces; The cycloaliphatic carboxylic acid's that aliphatic carboxylic acid and aliphatics replace lithium, sodium, potassium, calcium and magnesium salts; The subsalt of above-mentioned carboxylic acid (usually being called " high alkalinity carboxylate salt ") and many other similar oily molten organic acid basic metal and alkaline earth salts.Can use the mixture of the salt of two or more Different Alkali metals and/or alkaline-earth metal.Equally, also can use the salt (for example, one or more calcium phenylates and one or more calcium sulphonate) of the mixture of two or more different acid or two or more dissimilar acid.Though rubidium, caesium and strontium salt are feasible, their cost makes them use for great majority and becomes impracticable.
According to one embodiment of the invention, in early days cerium oxide nanoparticles is joined in the diesel-fuel by being incorporated in the diesel-fuel additive combination.Have been found that introduce particle in this way can be by preventing to reunite and preventing cerium particulate surface area losses thus and the fuel efficiency that in diesel engine, causes improving. the present invention embodies the above-mentioned performance that it is used for improving cerium oxide particle or nano particle more fully by making cerium oxide. this is to remove cerium by reducing owing to form throw out from fuel, thereby the cerium atom that keeps more can be used for combustion catalysis and reduce discharge or other benefit is realized.
Another benefit of the present invention is owing to having reduced or eliminated the precipitation that caused by the interaction between for example cerium atom or particle and fuel additive component and/or the pollutent, having separated out and/or the muddy filter stoppage that has reduced fuel filter.The fuel filter fault can cause the running of an engine difficulty, finally causes shutting down.An embodiment is that the interaction that reduces according to the present invention between phosphorus and cerium oxide particle or the nano particle reduces the fuel filter obstruction.The measurement of this benefit can be observed from the IP387 filtration test.Therefore, a kind of method that reduces the filter stoppage of fuel filter in the vehicles that use diesel engine or other device is provided herein, this diesel combustion diesel-fuel also has fuel filter, and described method is included in diesel-fuel is incorporated into the vehicles or the diesel-fuel additive combination of adding oxidation-containing cerium nano particle, washing composition and demulsifying compound in this fuel before of other device.
Therefore, the invention provides a kind of method that improves the efficient of combustion engine fuel, this method adds oxidation-containing cerium and/or the metallic substance that dissolves in fuel in manganese source and the washing composition and the demulsifying compound of the additive that acts as a fuel before being included in fuel being incorporated into the vehicles that comprise oil engine or other device in this fuel.In this way introduce cerium oxide need hardly or not for other introducing method as the required any vehicle fuel management system of dosing (on-board dosing) in using.Fuel efficiency is that cerium oxide particle is incorporated into result in the fuel.
Therefore, the present invention also provides a kind of fuel additive composition, its oxidation-containing cerium nano particle and/or manganese source and be preferably the washing composition of aliphatics succinimide and phosphorus less than the demulsifying compound of about 8 mg/kg.In another embodiment, fuel additive composition also contains demulsifying compound and the cetane number improver reagent as limiting above.
The concentration of cerium oxide particle or nano particle is generally in the diesel-fuel additive, by weight, and 0.1-10%, 0.5-5% usually.
The fuel dope of introducing at refinery generally can contain cetane number improver, cold flow improver, antioxidant and metal passivator.Therefore, fuel additive composition of the present invention can be introduced one or more in these.Therefore, the invention provides a kind of like this fuel additive composition, its oxidation-containing cerium nano particle and/or colloid, washing composition, demulsifying compound, randomly, be selected from cetane number improver (being also referred to as ignition improver) (for example alkyl nitrate ester selected), cold flow improver (for example polyester) and antioxidant (as phenoplast, for example 2,6-DI-tert-butylphenol compounds or phenylenediamine such as N, N '-di-sec-butyl-p-phenyl enediamine) and metal passivator such as salicyclic acid derivatives, N for example, N-two salicylidenes-1, one or more components in the 2-propylene diamine.
In diesel-fuel additive combination of the present invention, also can use slip additive, rust-preventive agent and defoamer.
In another embodiment of the invention, fuel additive composition can contain the demulsifying compound that mixture, blend, compound or the alloy of two or more metals and washing composition/dispersion agent and phosphorus are up to about 30 mg/kg.The mixed metal catalyst system is known, but needs and provide it at present to use with washing composition and demulsifying compound and can reduce or eliminate muddiness, unstable or precipitation.
Therefore, the improved fuel additive composition of the present invention can comprise that the material, washing composition/dispersion agent and the phosphorus that contain two or more metallic combustioncatalystss are up to the demulsifying compound of about 30 mg/kg.In another embodiment, this demulsifying compound has the phosphorus of the highest about 24 mg/kg, or in an independent embodiment, has the phosphorus of about 8 mg/kg-Yue 24 mg/kg, or In yet another embodiment, has the phosphorus of about 0.1 mg/kg-Yue 8 mg/kg.For example, washing composition/dispersion agent and demulsifying compound can be as described above.These metallic combustioncatalystss can be cerium oxide particle or nano particle, manganese source such as methyl cyclopentadienyl tricarbonyl manganese and source of iron such as dissolved ferric oxide and ferrocene." manganese " refers to any manganese or manganiferous material, compound or precursor herein, such as but not limited to
Figure S071A3476820070528D000071
Purchase methyl cyclopentadienyl tricarbonyl manganese and sulfonic acid manganese, phenol manganese, manganese salicylate, cyclopentadienyl tricarbonyl manganese, alkyl cyclopentadienyl manganese tricarbonyl, organic manganese tricarbonyl derivative, alkyl cyclopentadienyl manganese derivative, bicyclic pentadiene manganese, two alkyl cyclopentadienyl manganese, neutrality and high alkalinity bigcatkin willow acid manganese, neutrality and high alkalinity phenol manganese, neutrality and high alkalinity sulfonic acid manganese, manganese carboxylate, manganese oxide and their combination and mixture in Afton Chemical Corporation.
Therefore, can use cerium/manganese mixture or alloy in this article; Can use cerium/manganese/iron mixture or alloy in this article; Can use cerium/iron mixture or alloy in this article; Or can use manganese/iron mixture or alloy in this article.
A kind of fuel dope is provided, and its oxidation-containing cerium and manganese source, washing composition and phosphorus content mostly are the demulsifying compound of about 24 mg/kg most.In an independent embodiment, the phosphorus in the demulsifying compound is about 8 mg/kg-Yue 24 mg/kg, is the phosphorus of about 0.1 mg/kg-Yue 8 mg/kg In yet another embodiment.
And, also containing in the fuel additive composition of washing composition/dispersion agent and demulsifying compound in preparation, cerium oxide particle or nano particle can combine with ferrocene (source of iron).Therefore, for example provide a kind of fuel additive composition, its oxidation-containing cerium (Envirox of Oxonica for example TM), ferrocene (generally on sale), succinimide washing composition/dispersion agent (AftonChemical Corporation's
Figure S071A3476820070528D000081
4007, obtain by the 950MW polyisobutene and the polyamine reaction that have greater than 70% vinylidene and maleic anhydride, thereby realize that final N content is about 6.0%) and demulsifying compound (Tolad9357 of Baker Petrolite), said composition has excellent ignition dope activity, no muddiness or precipitation, good cigarette reduces and the fuel economy of raising.
Demonstration hybrid metal system
Embodiment 1
Cerium oxide (the Envirox of Oxonica for example TM) 1-200ppm
Ferrocene (generally on sale) 5-30wt%
Washing composition/dispersion agent be (Afton Chemical's
Figure S071A3476820070528D000082
5-15wt% 4007)
Demulsifying compound (Tolad9357 of Baker Petrolite) 1-10wt%
Aromatics and/or aliphatic solvent 45-89wt%
Embodiment 2
Cerium/manganese alloy 1-200ppm
Ferrocene (generally on sale) 5-30wt%
Washing composition/dispersion agent be (Afton Chemical's
Figure S071A3476820070528D000091
4007) 5-15wt%
Demulsifying compound (Tolad9357 of Baker Petrolite) 1-10wt%
Aromatics and/or aliphatic solvent 45-89wt%
Embodiment 3
Cerium/manganese/iron alloy 1-200ppm
Washing composition/dispersion agent be (Afton Chemical's 4007) 5-15wt%
Demulsifying compound (Tolad9357 of Baker Petrolite) 1-10wt%
Aromatics and/or aliphatic solvent 45-89wt%
Following embodiment has further set forth viewpoint of the present invention, but does not limit the present invention.
Embodiment:
Embodiment 1.
Figure S071A3476820070528D000093
4656 diesel-fuel additive (Afton ChemicalCorporation) based on the HR-PIB succinimide washing composition/dispersion agent with about 6.0 weight % nitrogen of the nitric acid 2-ethylhexyl cetane number improver of about 50% weight and 15% weight (available from Afton Chemical Corporation's
Figure S071A3476820070528D000094
4007).Will in aliphatic solvent
Figure S071A3476820070528D000095
4656 with the combination of the cerium oxide particle source of 250ppm with cerium oxide particle that 5ppm is provided (available from the Envirox of Oxonica TM).This combination can directly be used in diesel-fuel or dilute and the preparation diesel-fuel additive in aliphatics or aromatic solvent.
Embodiment 2. is for the fuel stability of the product that improves embodiment 1, demulsifying compound (available from the Tolad9338 of Baker Petrolite, the blend of the longer chain polyethylene glycols in Fatty Alcohol(C12-C14 and C12-C18) and aromatic solvent, oxyalkylated resol and oxyalkylated ethylene glycol/epoxy polymer adducts) combination with itself and 2.27% weight.The phosphorus content of Tolad9338 is 23.95 mg/kg.Yet, depend on the required storage time and/or relate to the type of diesel-fuel that have the turbidity of height, this all is unacceptable product concerning nearly all purposes.When filtering, obtain the throw out of per 1 kilogram of 1.39 gram.
Embodiment 3. is in order to improve fuel stability and solvability, with the product of embodiment 1 and the demulsifying compound of 2.27% weight (Tolad2898, the alkyl phenol resin than the-oxylization of low phosphorus content with 7.85 mg/kg) combination.Improved fuel stability, and reduced (seeing below), but be not for all fuel or all fuel purposes, all to be Utopian with respect to the turbidity as a result of embodiment 2.When filtering, obtain the throw out of per 1 kilogram of additive product, 0.35 gram.
Another kind of demulsifying compound (the Tolad9357 that embodiment 4. is 0.199 mg/kg with product and 2.27% weight, the phosphorus content of embodiment 1, yuban with 4-(1, the 1-dimethyl ethyl) phenol, propylene oxide and oxyethane in aromatic solvent) combination.This fuel dope combination has excellent transparency, low-down turbidity and unconspicuous throw out (per 1 kilogram of fuel dope combination is 0.15 gram throw out only).This diesel-fuel additive combination that will obtain under the processing rate of 1350ppm combines with diesel-fuel and causes excellent fuel stability, do not precipitate and do not have muddiness.In this final diesel-fuel product, cerium oxide content is 0.37 weight % (5ppm), so phosphorus content is a trace.This final diesel-fuel product is being excellent aspect the burning of cigarette minimizing, fuel economy, fuel stability, solvability and raising.
As what can find out from top embodiment, when
Figure S071A3476820070528D000101
4656 diesel-fuel additive (alkyl nitrate ester selected cetane number improver) and Tolad9338 demulsifying compound and Enivrox TMWhen cerium oxide nanoparticles was mixed, the fuel dope product that obtains produced the throw out of per 1 kilogram of additive, 1.39 grams.When
Figure S071A3476820070528D000102
4656 diesel-fuel additive (alkyl nitrate ester selected cetane number improver) and Tolad2898 demulsifying compound and Enivrox TMWhen cerium oxide nanoparticles was mixed, product produced the throw out of per 1 kilogram of additive, 0.35 gram.When
Figure S071A3476820070528D000103
4656 diesel-fuel additive (alkyl nitrate ester selected cetane number improver) and Tolad9357 demulsifying compound and Enivrox TMDuring mixing, product produces the throw out of per 1 kilogram of additive, 0.15 gram.
Turbidimetry
Figure S071A3476820070528D000104
4656 and Tolad9338 and Enivrox TMMix the turbidity that produces 1552NTU.
Figure S071A3476820070528D000105
4656 and Tolad2898 and Enivrox TMMix the turbidity that produces 880NTU.
4656 and Tolad9357 and Enivrox TMMix the turbidity that produces 175NTU.
(NTU is commonly referred to as " non-arbitrary unit " in industry).Significantly, when combination cetane number improver, cerium oxide nanoparticles and phosphorous low demulsifying compound, unexpected improvement is that turbidity reduces.
Figure S071A3476820070528D000107
Figure S071A3476820070528D000111
In addition, the applicant has carried out the froth breaking test to the fuel dope product of making, have astonishing result that contains alkyl nitrate ester selected cetane number improver and cerium oxide nanoparticles.Minimizing has active influence to foam to observe cerium oxide.Use Envirox separately TMProduct, the fuel foam attenuation time reduces by half, but when with
Figure S071A3476820070528D000112
When 4656 type products used jointly, the foaming properties improvement had surpassed common
Figure S071A3476820070528D000113
4656 foaming properties.Therefore, when combination cerium oxide nanoparticles and alkyl nitrate ester selected cetane number improver, obtaining unexpected benefit aspect the minimizing of diesel-fuel foam.
Froth breaking experiment general introduction
Basis reference diesel-fuel has 45 seconds fall time and the foam height of 100mls;
Use 250ppm Envirox TMThe diesel-fuel of handling has 21.2 seconds fall time and the foam height of 100mls;
Use 1100ppm
Figure S071A3476820070528D000114
4656 diesel-fuels of handling have 6.9 seconds fall time and the foam height of 80mls;
Use 250ppm Envirox TMAdd 1100ppm
Figure S071A3476820070528D000115
4656 diesel engine of handling have 2.8 seconds fall time and 55mls foam height.
Significantly, for the foam minimizing that realizes by combination cerium oxide nanoparticles and alkyl nitrate ester selected cetane number improver in diesel-fuel unexpected excellent the improvement arranged.Therefore, the method that provides a kind of diesel-fuel foam to reduce by the fuel dope combination that oxidation-containing cerium nano particle and alkyl nitrate ester selected cetane improver additive are provided for fuel herein.
By the present invention being incorporated into the remarkable improvement that used Machine Design and method are provided in the vehicles or the equipment.In one embodiment, provide a kind of emission control system that is used for aftertreatment diesel-fuel combustion processes exhaust flow herein, comprising: exhaust passageway is used for by containing the exhaust flow from diesel-fuel incendiary waste by-product; Particulate filter is selected from cyclic regeneration technology diesel particulate filter, diesel particulate filter and catalyzed diesel, is positioned at exhaust passageway and is suitable for contacting with exhaust flow; Wherein fuel has introducing additive combination wherein, and this additive combination oxidation-containing cerium and/or manganese, washing composition, alkyl nitrate ester selected cetane number improver and optional demulsifying compound are thus by making the dispersed maximum running that improves particulate filter of cerium oxide.This has prevented the reunion of cerium oxide particle, otherwise reunion reduces the interaction of cerium oxide and exhaust gas particle.And the dispersion of the cerium oxide particle of raising of the present invention has reduced their reunion, and makes the minimum or elimination of fuel filter possibility of jamming.In addition, also provide a kind of process useful that improves the diesel particulate filter performance: under the situation of not using fuel dope combination described herein, reduce negative impact to filter surfaces.
In some engine design, injector spray orifice right and wrong are columniform, but open outside the combustion chamber along with diameter increases, and purpose is behind each fuel injection injector holes to be kept dry.Find that these designs extremely are easy to coking, fuel flows, the incendiary homogeneity and the coking meeting influences negatively, and impels settling to gather, and the surface of injector holes can not be purged totally because fuel dynamics flows.Therefore, exist protect the needs of injector spray orifice by the exposure that the combustion chamber gas that comprises cerium atom and cerium oxide particle is at present improved.By the present invention, cerium and cerium oxide particle can be used for oxidation and remove carbonaceous sediment around the spray orifice neutralization. therefore, this paper provides a kind of diesel-fuel additive to be combined in the method for using in the diesel engine with non-cylindrical injector spray orifice, and this diesel-fuel additive combination oxidation-containing cerium, washing composition/dispersion agent, phosphorus are less than the demulsifying compound of 24 mg/kg.In an independent embodiment, the phosphorus in the demulsifying compound is about 8 mg/kg-Yue 24 mg/kg, is the phosphorus of about 0.1 mg/kg-Yue 8 mg/kg In yet another embodiment.
In sum, the present invention relates to following technical scheme:
1. the diesel-fuel additive combination that in this fuel, adds oxidation-containing cerium nano particle, washing composition/dispersion agent and demulsifying compound before method that improves diesel fuel for internal combustion engines machine fuel efficiency, this method are included in and are incorporated into fuel in the vehicles that comprise oil engine or other device.
2. the method for scheme 1, wherein washing composition/dispersion agent exists with the amount of the about 20 weight % of about 5-in the additive combination.
3. the method for scheme 1, wherein washing composition/dispersion agent is selected from succinimide, acid amides, amine, Mannich base and the polyetheramine of alkenyl substituted.
4. the method for scheme 1, wherein additive combination also contains one or more materials that are selected from cetane number improver and the metal deactivators.
5. the method for scheme 1, wherein additive combination also contains the manganese source.
6. the method for scheme 1, wherein additive combination also contains the alkyl phenol resin that is selected from-oxylization and has demulsifying compound in yuban, propylene oxide and the oxyethane of 4-(1, the 1-dimethyl ethyl) phenol.
7. the method for scheme 1, wherein the phosphorus content of demulsifying compound mostly is about 24 mg/kg most.
8. the method for scheme 1, wherein the phosphorus content of demulsifying compound is about 8 mg/kg-Yue 24 mg/kg.
9. the method for scheme 1, wherein the phosphorus content of demulsifying compound is about 0.1 mg/kg-Yue 8 mg/kg.
10. the method for scheme 1, wherein the phosphorus content of demulsifying compound is about 0.2 mg/kg.
11. the method for scheme 1, wherein fuel dope contains 1-200ppm, particle diameter is the cerium oxide nanoparticles of about 300 nanometers of 1-; 5-15 weight %, be selected from the washing composition/dispersion agent in alkylating succinimide, Mannich base, acid amides, amine and the polyetheramine; With 1-10 weight %, be selected from the alkyl phenol resin of-oxylization and have demulsifying compound in yuban, propylene oxide and the oxyethane of 4-(1, the 1-dimethyl ethyl) phenol, wherein the phosphorus content of demulsifying compound is less than 8 mg/kg.
12. the method for scheme 1, wherein washing composition/dispersion agent comprises the alkali metal containing that dissolves in fuel or the washing composition of alkaline-earth metal.
13. a fuel dope, its oxidation-containing cerium and/or manganese source and washing composition.
14. according to the fuel dope of scheme 13, wherein the concentration of cerium oxide and/or manganese is 0.1-10% weight.
15. according to the fuel dope of scheme 13, wherein the concentration of cerium oxide nanoparticles and/or manganese is 0.5-5% weight.
16. according to the fuel dope of scheme 13, wherein washing composition is the nitrogenous ashless detergent of alkalescence.
17. according to the fuel dope of scheme 13, wherein washing composition is the succinimide that each molecule on average has at least 3 nitrogen-atoms.
18. according to the fuel dope of scheme 13, wherein succinimide is to be formed with the alkylene polyamine mixture that each molecule on average has at least 3 nitrogen-atoms by the alkyl or alkenyl amber acylation agent that has at least 35 carbon atoms in the alkyl or alkenyl part.
19. fuel dope according to scheme 13; wherein succinimide is by can being 500-10 by number-average molecular weight, the polyisobutenyl amber acylation agent that 000 polyisobutene obtains and have that the ethylidene polyamines of the average composition from the Triethylenetetramine (TETA) to the penten forms.
20. according to the fuel dope of scheme 13, wherein the molecular weight of the aliphatic chain of succinimide is 500-2500.
21. according to the fuel dope of scheme 13, wherein the molecular weight of the aliphatic chain of succinimide is 750-1500.
22. according to each fuel dope among the scheme 13-21, it also contains one or more materials that are selected from cleaning agent, defoamer, ignition improver, rust-preventive agent, perfume compound, antioxidant, metal passivator, lubricant and the demulsifying compound.
23. according to the fuel dope of scheme 13, its fatty hydrocarbon or aromatic hydrocarbons or Fatty Alcohol(C12-C14 and C12-C18) solvent.
24. in this fuel, add the diesel-fuel additive combination of oxidation-containing cerium nano particle, washing composition and demulsifying compound before a method that improves diesel-fuel stability, described method are included in and introduce fuel in the vehicles that comprise oil engine or other device.
25. one kind is improved incendiary method in the diesel engine, adds the diesel-fuel additive combination of oxidation-containing cerium nano particle, washing composition and demulsifying compound before described method is included in and introduces fuel in the vehicles that comprise oil engine or other device in this fuel.
26. method that reduces cigarette in the diesel combustion, described method comprises the method that improves diesel-fuel stability, adds the diesel-fuel additive combination of oxidation-containing cerium nano particle, washing composition and demulsifying compound before described method is included in and introduces fuel in the vehicles that comprise oil engine or other device in this fuel.
27. one kind is improved the deliquescent method of organo-metallic fuel dope in diesel-fuel, adds the diesel-fuel additive combination of oxidation-containing cerium nano particle, washing composition and demulsifying compound before described method is included in and introduces fuel in the vehicles that comprise oil engine or other device in this fuel.
28. a reduction has the method for turbidity in the diesel-fuel of diesel-dope, adds the diesel-fuel additive combination of oxidation-containing cerium nano particle, washing composition and demulsifying compound before described method is included in and introduces fuel in the vehicles that comprise oil engine or other device in this fuel.
29. the method for the filter stoppage of fuel filter in vehicles that reduce to use diesel engine or other device, this diesel combustion diesel-fuel also has fuel filter, and described method is included in fuel is incorporated into the vehicles or the diesel-fuel additive combination of adding oxidation-containing cerium nano particle, washing composition and demulsifying compound in diesel-fuel before of other device.
30. a method that improves the fuel dope deemulsification comprises adding cerium oxide nanoparticles, washing composition and demulsifying compound that in fuel dope wherein demulsifying compound has the phosphorus less than about 30 mg/kg.
31. improvement fuel additive composition of the present invention, it can comprise that material, washing composition/dispersion agent and the phosphorus of the combustioncatalysts that contains two or more metals are up to the demulsifying compound of about 30 mg/kg.
32. one kind is reduced foamy method in the diesel-fuel, described method is included as the fuel dope combination that fuel provides oxidation-containing cerium nano particle and alkyl nitrate ester selected cetane improver additive.
33. an emission control that is used for aftertreatment diesel-fuel combustion processes exhaust flow comprises:
Exhaust passageway is used for by containing the exhaust flow from diesel-fuel incendiary waste by-product,
Oxide catalyst,
Particulate filter is selected from cyclic regeneration technology diesel particulate filter, diesel particulate filter and catalyzed diesel, and be positioned at exhaust passageway and be suitable for contacting with exhaust flow,
Wherein, fuel has introducing additive combination wherein, and this additive combination oxidation-containing cerium and/or manganese, washing composition, alkyl nitrate ester selected ignition improver and optional demulsifying compound improve the running of particulate filter thus.
34. a raising is used for the method for the emission control of aftertreatment diesel-fuel combustion processes exhaust flow, comprising:
Exhaust passageway is used for by containing the exhaust flow from diesel-fuel incendiary waste by-product,
Particulate filter is selected from cyclic regeneration technology diesel particulate filter, diesel particulate filter and catalyzed diesel, and be positioned at exhaust passageway and be suitable for contacting with exhaust flow,
Wherein, fuel has introducing additive combination wherein, and this additive combination oxidation-containing cerium and/or manganese, washing composition, alkyl nitrate ester selected ignition improver and optional demulsifying compound improve the running of particulate filter thus.
35. oxidation-containing cerium, washing composition/dispersion agent, phosphorus content are less than the application of diesel-fuel additive in the diesel engine with non-cylindrical injector spray orifice of the demulsifying compound of 24 mg/kg.
According to the consideration of specification sheets and the practice of the disclosure of disclosure herein, other embodiment of this specification sheets is apparent to those skilled in the art.When using in specification sheets and claim, " one " can refer to a kind of or a kind of incessantly.Unless otherwise stated, otherwise all numerals that are expressed as dosis refracta, performance such as molecular weight, per-cent, ratio, reaction conditions etc. of in specification sheets and claims, using be interpreted as under any circumstance all regulating by term " about ".Therefore, unless show on the contrary, the digital parameters of stating in specification sheets and claims all is can be according to the approximation of planning to change by the desired properties that the present invention obtains.At least, rather than attempt to limit the application of the principle that is equivalent to claims scope, each digital parameters all should be regarded as at least considering report significant figure number and by using the common method of rounding up makes up.Although the digital scope and the parameter of the scope statement that the present invention is wide are approximations, the numerical value of stating in the specific embodiment is still as far as possible accurately reported.Yet any numerical value must contain some error that is produced by the standard deviation of finding in their experimental measurements separately.It is exemplary that the meaning only is considered as specification sheets and embodiment, and the real scope and spirit in this aspect are to be shown by following claim.

Claims (10)

1. method that improves diesel fuel for internal combustion engines machine fuel efficiency, this method adds the diesel-fuel additive combination before being included in and being incorporated into fuel in the vehicles that comprise oil engine or other device in this fuel, described diesel-fuel additive combination comprises:
Additive, it is selected from mixture, cerium/manganese alloy nano particle, the cerium/manganese/iron alloy nano particle in cerium oxide nanoparticles and manganese source;
Washing composition/dispersion agent; With
Demulsifying compound, it has the phosphorus of about 0.1mg/kg to about 24mg/kg,
Wherein the concentration of cerium oxide nanoparticles or alloy nanoparticle is 0.1-10wt%, and the concentration in manganese source is 0.1-10wt%.
2. the process of claim 1 wherein that washing composition/dispersion agent in the additive combination exists with the amount of the about 20 weight % of about 5-.
3. the process of claim 1 wherein that washing composition/dispersion agent is selected from the succinimide of alkenyl substituted, acid amides, amine, Mannich base and polyetheramine.
4. the process of claim 1 wherein that additive combination also contains the manganese source.
5. the process of claim 1 wherein that additive combination also contains the demulsifying compound in the alkyl phenol resin that is selected from-oxylization and yuban, propylene oxide and the oxyethane with 4-(1, the 1-dimethyl ethyl) phenol.
6. the process of claim 1 wherein that the phosphorus content of demulsifying compound mostly is about 24 mg/kg most.
7. the process of claim 1 wherein that fuel dope contains 1-200ppm, particle diameter is the cerium oxide nanoparticles of about 300 nanometers of 1-; 5-15 weight %, be selected from the washing composition/dispersion agent in alkylating succinimide, Mannich base, acid amides, amine and the polyetheramine; With 1-10 weight %, be selected from the alkyl phenol resin of-oxylization and have demulsifying compound in yuban, propylene oxide and the oxyethane of 4-(1, the 1-dimethyl ethyl) phenol, wherein the phosphorus content of demulsifying compound is less than 8 mg/kg.
8. fuel dope, it contains
Additive, it is selected from mixture, cerium/manganese alloy nano particle, the cerium/manganese/iron alloy nano particle in cerium oxide nanoparticles and manganese source;
Washing composition; With
Demulsifying compound, it has the phosphorus of about 0.1mg/kg to about 24mg/kg,
Wherein the concentration of cerium oxide nanoparticles or alloy nanoparticle is 0.1-10wt%, and the concentration in manganese source is 0.1-10wt%.
9. a method that improves diesel-fuel stability adds diesel-fuel additive before described method is included in and introduces fuel in the vehicles that comprise oil engine or other device and makes up in this fuel, and described diesel-fuel additive combination comprises:
Additive, it is selected from mixture, cerium/manganese alloy nano particle, the cerium/manganese/iron alloy nano particle in cerium oxide nanoparticles and manganese source;
Washing composition; With
Demulsifying compound, it has the phosphorus of about 0.1mg/kg to about 24mg/kg,
Wherein the concentration of cerium oxide nanoparticles or alloy nanoparticle is 0.1-10wt%, and the concentration in manganese source is 0.1-10wt%.
10. one kind is improved incendiary method in the diesel engine, and described method adds the diesel-fuel additive combination before being included in and introducing fuel in the vehicles that comprise oil engine or other device in this fuel, and described diesel-fuel additive combination comprises:
Additive, it is selected from mixture, cerium/manganese alloy nano particle, the cerium/manganese/iron alloy nano particle in cerium oxide nanoparticles and manganese source;
Washing composition; With
Demulsifying compound, it has the phosphorus of about 0.1mg/kg to about 24mg/kg,
Wherein the concentration of cerium oxide nanoparticles or alloy nanoparticle is 0.1-10wt%, and the concentration in manganese source is 0.1-10wt%.
CN2007101034768A 2006-09-19 2007-05-18 Diesel fuel additives containing cerium or manganese and detergents Expired - Fee Related CN101148618B (en)

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